{2-[2-(Piperidin-1-yl)ethyl­imino­methyl]phenolato-κ³N,N′,O}(thio­cyanato-κN)nickel(II)

In the title compound, [Ni(C₁₄H₁₉N₂O)(NCS)], a mononuclear Schiff base nickel(II) complex, the Ni atom is four-coordinated by one imine N atom, one amine N atom and one phenolate O atom of the Schiff base ligand, and by one terminal N atom of the thio­cyanate ligand, forming a square-planar geometry. The piperidine ring adopts a chair conformation. No significant hydrogen bonding or π–π inter­actions are observed in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.107
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C15     ..       6.10 su

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (3)       2.75

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Nickel(II) complexes derived from Schiff base ligands have been studied extensively due to their interesting structures and numerous applications (Mukhopadhyay et al., 2003; Kraihanzel et al., 1981; Di Bella et al., 1997; Loeb et al., 1984; Costes et al., 2005). Previously, the author has reported the crystal structure of a Schiff base zinc(II) complex (Wang, 2007). As part of a further investigation of Schiff base complexes, the structure of the title compound, a mononuclear nickel(II) complex, is reported here.

The square-planar coordination environment of Ni^II atom in the title compound is formed by one imine N atom, one amine N atom, and one phenolate O atom of the Schiff base ligand, and by one terminal N atom of the thiocyanate ligand (Fig. 1). The coordination bond distances (Table 1) are typical and comparable with the values in similar nickel(II) complexes (Zhu et al., 2004; Liu et al., 2006; Fu et al., 2007).

Related literature

For related literature, see: Costes et al. (2005); Di Bella et al. (1997); Fu et al. (2007); Kraihanzel et al. (1981); Liu et al. (2006); Loeb et al. (1984); Mukhopadhyay et al. (2003); Wang (2007); Zhu et al. (2004).

S2. Experimental

The title compound was obtained by stirring of salicylaldehyde (0.1 mmol, 12.1 mg), 2-piperidin-1-ylethylamine (0.1 mmol, 12.8 mg), ammonium thiocyanate (0.1 mmol, 7.6 mg), and nickel(II) nitrate (0.1 mmol, 29.1 mg) in methanol (20 ml) for 30 min. The reaction mixture was then filtered. Red block-shaped single crystals suitable for X-ray diffraction were formed from the filtrate after 5 d.

S3. Refinement

H atoms were positioned geometrically (C—H = 0.93 or 0.97 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of title compound, showing the numbering scheme and displacement ellipsoids drawn at the 30% probability level

{2-[2-(Piperidin-1-yl)ethyliminomethyl]phenolato-κ³N,N',O}(thiocyanato- κN)nickel(II)

Crystal data

[Ni(C14H19N2O)(NCS)]	F(000) = 1456
Mr = 348.10	Dx = 1.465 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3068 reflections
a = 12.997 (3) Å	θ = 2.5–25.4°
b = 12.525 (3) Å	µ = 1.36 mm^−1
c = 19.386 (4) Å	T = 298 K
V = 3155.8 (11) Å^3	Block, red
Z = 8	0.37 × 0.32 × 0.30 mm

Data collection

Bruker SMART APEX area-detector diffractometer	3587 independent reflections
Radiation source: fine-focus sealed tube	2494 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.618, Tmax = 0.670	k = −16→16
18388 measured reflections	l = −16→25

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0516P)^2] where P = (Fo^2 + 2Fc^2)/3
3587 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.11596 (2)	0.56364 (3)	0.162861 (19)	0.03658 (13)
S1	−0.00585 (8)	0.49582 (7)	0.38329 (4)	0.0652 (3)
O1	0.05319 (15)	0.43892 (14)	0.13658 (11)	0.0459 (5)
N1	0.18173 (17)	0.58278 (17)	0.07974 (12)	0.0409 (6)
N2	0.18420 (15)	0.69534 (17)	0.19361 (12)	0.0373 (5)
N3	0.05700 (18)	0.54126 (18)	0.25004 (14)	0.0465 (6)
C1	0.1120 (2)	0.4304 (2)	0.01950 (16)	0.0428 (7)
C2	0.0550 (2)	0.3924 (2)	0.07622 (15)	0.0382 (6)
C3	−0.0010 (2)	0.2974 (2)	0.06736 (16)	0.0455 (7)
H3	−0.0393	0.2707	0.1040	0.055*
C4	−0.0004 (2)	0.2436 (2)	0.00622 (16)	0.0508 (8)
H4	−0.0379	0.1807	0.0021	0.061*
C5	0.0552 (2)	0.2813 (3)	−0.05009 (17)	0.0563 (9)
H5	0.0552	0.2442	−0.0917	0.068*
C6	0.1096 (2)	0.3739 (3)	−0.04300 (16)	0.0523 (8)
H6	0.1461	0.4001	−0.0806	0.063*
C7	0.1740 (2)	0.5242 (2)	0.02556 (16)	0.0462 (7)
H7	0.2119	0.5446	−0.0129	0.055*
C8	0.2543 (2)	0.6728 (2)	0.07842 (17)	0.0511 (8)
H8A	0.2566	0.7043	0.0327	0.061*
H8B	0.3229	0.6487	0.0905	0.061*
C9	0.2168 (2)	0.7523 (2)	0.12972 (14)	0.0475 (7)
H9A	0.1591	0.7917	0.1107	0.057*
H9B	0.2712	0.8026	0.1405	0.057*
C10	0.2741 (2)	0.6595 (2)	0.23558 (16)	0.0450 (7)
H10A	0.3201	0.6186	0.2063	0.054*
H10B	0.2497	0.6123	0.2718	0.054*
C11	0.3344 (2)	0.7504 (3)	0.26836 (16)	0.0535 (8)
H11A	0.3669	0.7925	0.2325	0.064*
H11B	0.3881	0.7212	0.2975	0.064*
C12	0.2646 (2)	0.8218 (3)	0.31126 (18)	0.0597 (9)
H12A	0.2378	0.7822	0.3503	0.072*
H12B	0.3035	0.8822	0.3287	0.072*
C13	0.1766 (2)	0.8611 (2)	0.26675 (17)	0.0512 (8)
H13A	0.1302	0.9040	0.2945	0.061*
H13B	0.2034	0.9058	0.2301	0.061*
C14	0.11822 (19)	0.7684 (2)	0.23584 (16)	0.0422 (7)
H14A	0.0868	0.7277	0.2728	0.051*
H14B	0.0634	0.7961	0.2070	0.051*
C15	0.0307 (2)	0.5216 (2)	0.30525 (16)	0.0405 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0351 (2)	0.0358 (2)	0.0388 (2)	−0.00503 (14)	0.00431 (15)	0.00423 (16)
S1	0.0955 (7)	0.0548 (5)	0.0454 (5)	0.0077 (5)	0.0229 (5)	0.0067 (4)
O1	0.0569 (13)	0.0419 (11)	0.0388 (12)	−0.0127 (9)	0.0085 (10)	0.0004 (9)
N1	0.0376 (12)	0.0401 (13)	0.0448 (15)	−0.0040 (10)	0.0058 (11)	0.0084 (11)
N2	0.0307 (11)	0.0364 (12)	0.0448 (14)	−0.0035 (9)	0.0010 (10)	0.0048 (11)
N3	0.0522 (15)	0.0421 (14)	0.0451 (16)	−0.0119 (11)	0.0063 (12)	0.0000 (12)
C1	0.0447 (16)	0.0452 (17)	0.0386 (17)	0.0032 (13)	0.0001 (13)	0.0036 (14)
C2	0.0373 (14)	0.0391 (15)	0.0380 (17)	0.0060 (12)	−0.0026 (12)	0.0036 (13)
C3	0.0475 (16)	0.0443 (16)	0.0448 (18)	−0.0041 (13)	−0.0035 (14)	0.0025 (15)
C4	0.0528 (17)	0.0485 (18)	0.051 (2)	−0.0015 (15)	−0.0117 (16)	−0.0030 (16)
C5	0.066 (2)	0.060 (2)	0.042 (2)	0.0033 (17)	−0.0084 (16)	−0.0080 (16)
C6	0.0557 (18)	0.064 (2)	0.0369 (18)	0.0027 (16)	0.0013 (14)	0.0019 (16)
C7	0.0455 (17)	0.0488 (17)	0.0441 (18)	0.0010 (14)	0.0128 (14)	0.0110 (15)
C8	0.0512 (17)	0.0498 (19)	0.052 (2)	−0.0133 (14)	0.0111 (15)	0.0096 (15)
C9	0.0443 (16)	0.0425 (16)	0.056 (2)	−0.0094 (13)	0.0004 (14)	0.0098 (16)
C10	0.0353 (14)	0.0427 (16)	0.057 (2)	0.0033 (12)	−0.0036 (13)	0.0043 (14)
C11	0.0348 (14)	0.063 (2)	0.062 (2)	−0.0071 (14)	−0.0099 (14)	0.0069 (18)
C12	0.0524 (19)	0.061 (2)	0.066 (2)	−0.0174 (16)	−0.0054 (16)	−0.0108 (17)
C13	0.0463 (16)	0.0372 (16)	0.070 (2)	−0.0025 (13)	0.0010 (16)	−0.0051 (15)
C14	0.0330 (13)	0.0384 (16)	0.055 (2)	0.0009 (11)	−0.0015 (13)	−0.0005 (14)
C15	0.0441 (15)	0.0291 (14)	0.0484 (19)	−0.0019 (12)	0.0036 (14)	−0.0033 (14)

Geometric parameters (Å, º)

Ni1—O1	1.8344 (19)	C6—H6	0.93
Ni1—N1	1.840 (2)	C7—H7	0.93
Ni1—N3	1.877 (3)	C8—C9	1.490 (4)
Ni1—N2	1.965 (2)	C8—H8A	0.97
S1—C15	1.619 (3)	C8—H8B	0.97
O1—C2	1.307 (3)	C9—H9A	0.97
N1—C7	1.285 (4)	C9—H9B	0.97
N1—C8	1.470 (3)	C10—C11	1.521 (4)
N2—C9	1.491 (3)	C10—H10A	0.97
N2—C10	1.493 (3)	C10—H10B	0.97
N2—C14	1.498 (3)	C11—C12	1.522 (4)
N3—C15	1.150 (3)	C11—H11A	0.97
C1—C6	1.404 (4)	C11—H11B	0.97
C1—C2	1.409 (4)	C12—C13	1.515 (4)
C1—C7	1.429 (4)	C12—H12A	0.97
C2—C3	1.405 (4)	C12—H12B	0.97
C3—C4	1.363 (4)	C13—C14	1.511 (4)
C3—H3	0.93	C13—H13A	0.97
C4—C5	1.392 (4)	C13—H13B	0.97
C4—H4	0.93	C14—H14A	0.97
C5—C6	1.365 (4)	C14—H14B	0.97
C5—H5	0.93
O1—Ni1—N1	94.26 (10)	N1—C8—H8B	110.3
O1—Ni1—N3	86.63 (9)	C9—C8—H8B	110.3
N1—Ni1—N3	176.32 (10)	H8A—C8—H8B	108.6
O1—Ni1—N2	178.33 (9)	C8—C9—N2	109.1 (2)
N1—Ni1—N2	86.94 (10)	C8—C9—H9A	109.9
N3—Ni1—N2	92.09 (10)	N2—C9—H9A	109.9
C2—O1—Ni1	128.31 (18)	C8—C9—H9B	109.9
C7—N1—C8	118.3 (2)	N2—C9—H9B	109.9
C7—N1—Ni1	127.2 (2)	H9A—C9—H9B	108.3
C8—N1—Ni1	114.41 (19)	N2—C10—C11	113.9 (2)
C9—N2—C10	112.0 (2)	N2—C10—H10A	108.8
C9—N2—C14	108.9 (2)	C11—C10—H10A	108.8
C10—N2—C14	109.5 (2)	N2—C10—H10B	108.8
C9—N2—Ni1	106.12 (17)	C11—C10—H10B	108.8
C10—N2—Ni1	105.41 (16)	H10A—C10—H10B	107.7
C14—N2—Ni1	114.86 (15)	C10—C11—C12	111.2 (2)
C15—N3—Ni1	172.4 (2)	C10—C11—H11A	109.4
C6—C1—C2	119.4 (3)	C12—C11—H11A	109.4
C6—C1—C7	119.9 (3)	C10—C11—H11B	109.4
C2—C1—C7	120.7 (3)	C12—C11—H11B	109.4
O1—C2—C3	118.5 (3)	H11A—C11—H11B	108.0
O1—C2—C1	123.9 (3)	C13—C12—C11	109.3 (3)
C3—C2—C1	117.6 (3)	C13—C12—H12A	109.8
C4—C3—C2	121.5 (3)	C11—C12—H12A	109.8
C4—C3—H3	119.3	C13—C12—H12B	109.8
C2—C3—H3	119.3	C11—C12—H12B	109.8
C3—C4—C5	121.1 (3)	H12A—C12—H12B	108.3
C3—C4—H4	119.4	C14—C13—C12	110.8 (2)
C5—C4—H4	119.4	C14—C13—H13A	109.5
C6—C5—C4	118.6 (3)	C12—C13—H13A	109.5
C6—C5—H5	120.7	C14—C13—H13B	109.5
C4—C5—H5	120.7	C12—C13—H13B	109.5
C5—C6—C1	121.8 (3)	H13A—C13—H13B	108.1
C5—C6—H6	119.1	N2—C14—C13	113.5 (2)
C1—C6—H6	119.1	N2—C14—H14A	108.9
N1—C7—C1	125.5 (3)	C13—C14—H14A	108.9
N1—C7—H7	117.3	N2—C14—H14B	108.9
C1—C7—H7	117.3	C13—C14—H14B	108.9
N1—C8—C9	106.9 (2)	H14A—C14—H14B	107.7
N1—C8—H8A	110.3	N3—C15—S1	179.2 (3)
C9—C8—H8A	110.3